Syntheses and Properties of Multiferrocenylated Corannulenes
Berit Topolinski
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34–36, 14195 Berlin, Germany, http://www.bcp.fu-berlin.de/chemie/
Search for more papers by this authorBernd M. Schmidt
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34–36, 14195 Berlin, Germany, http://www.bcp.fu-berlin.de/chemie/
Present address: Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany
Search for more papers by this authorSergej Schwagerus
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34–36, 14195 Berlin, Germany, http://www.bcp.fu-berlin.de/chemie/
Search for more papers by this authorMichael Kathan
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34–36, 14195 Berlin, Germany, http://www.bcp.fu-berlin.de/chemie/
Search for more papers by this authorCorresponding Author
Dieter Lentz
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34–36, 14195 Berlin, Germany, http://www.bcp.fu-berlin.de/chemie/
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34–36, 14195 Berlin, GermanySearch for more papers by this authorBerit Topolinski
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34–36, 14195 Berlin, Germany, http://www.bcp.fu-berlin.de/chemie/
Search for more papers by this authorBernd M. Schmidt
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34–36, 14195 Berlin, Germany, http://www.bcp.fu-berlin.de/chemie/
Present address: Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany
Search for more papers by this authorSergej Schwagerus
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34–36, 14195 Berlin, Germany, http://www.bcp.fu-berlin.de/chemie/
Search for more papers by this authorMichael Kathan
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34–36, 14195 Berlin, Germany, http://www.bcp.fu-berlin.de/chemie/
Search for more papers by this authorCorresponding Author
Dieter Lentz
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34–36, 14195 Berlin, Germany, http://www.bcp.fu-berlin.de/chemie/
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34–36, 14195 Berlin, GermanySearch for more papers by this authorGraphical Abstract
The synthesis and properties of corannulenes bearing up to five ferrocenyl groups are described. All compounds were investigated electrochemically to elucidate the interactions in the multiferrocenylated corannulenes. Additionally, several molecular structures were confirmed by single-crystal X-ray analyses and are discussed with respect to those of previously studied corannulenes.
Abstract
The syntheses and properties of corannulenes bearing different numbers and types of ferrocenyl groups are described. Six different monoferrocenylated corannulenes were synthesized, and the crystal structure of 1-corannulenyl-1′-(ferrocenyl)benzene was elucidated by single-crystal X-ray analysis. Further, diferrocenylated corannulenes bearing methyl or trifluoromethyl groups are reported. Buckybowls with four and five ferrocenyl substituents were synthesized from tetrabromocorannulene and the symmetrical pentachlorocorannulene. The molecular structure and nutshell-like crystal packing of a tetraferrocenylated corannulene was determined by single-crystal X-ray analysis. Additionally, all compounds presented herein were subjected to electrochemical and optical measurements in solution.
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References
- 1
- 1a Y.-T. Wu , J. S. Siegel , Chem. Rev. 2006 , 106 , 4843 –4867 .
- 1b V. M. Tsefrikas , L. T. Scott , Chem. Rev. 2006 , 106 , 4868 –4884 .
- 1c A. Sygula , Eur. J. Org. Chem. 2011 , 1611 –1625 .
- 1d M. Stępień , Synlett 2013 , 24 , 1316 –1321 .
- 2
- 2a S. Higashibayashi , S. Onogi , H. K. Srivastava , G. N. Sastry , Y.-T. Wu , H. Sakurai , Angew. Chem. Int. Ed. 2013 , 52 , 7314 –7316 .
- 2b S. Mebs , M. Weber , P. Luger , B. M. Schmidt , H. Sakurai , S. Higashibayashi , S. Onogi , D. Lentz , Org. Biomol. Chem. 2012 , 10 , 2218 –2222 .
- 3
- 3a W. E. Barth , R. G. Lawton , J. Am. Chem. Soc. 1966 , 88 , 380 –381 .
- 3b R. G. Lawton , W. E. Barth , J. Am. Chem. Soc. 1971 , 93 , 1730 –1745 .
- 4
- 4a L. T. Scott , M. M. Hashemi , M. S. Bratcher , J. Am. Chem. Soc. 1992 , 114 , 1920 –1921 .
- 4b T. J. Seiders , K. K. Baldridge , G. H. Grube , J. S. Siegel , J. Am. Chem. Soc. 2001 , 123 , 517 –525 .
- 4c T. Hayama , K. K. Baldridge , Y.-T. Wu , A. Linden , J. S. Siegel , J. Am. Chem. Soc. 2008 , 130 , 1583 –1591 .
- 5 B. M. Schmidt , D. Lentz , Chem. Lett. 2014 , 43 , 171 –177 .
- 6
- 6a D. Eisenberg , J. M. Quimby , E. A. Jackson , L. T. Scott , R. Shenhar , Chem. Commun. 2010 , 46 , 9010 –9012 .
- 6b I. Aprahamian , D. Eisenberg , R. E. Hoffman , T. Sternfeld , Y. Matsuo , E. A. Jackson , E. Nakamura , L. T. Scott , T. Sheradsky , M. Rabinovitz , J. Am. Chem. Soc. 2005 , 127 , 9581 –9587 .
- 6c R. Benshafrut , E. Shabtai , M. Rabinovitz , L. T. Scott , Eur. J. Org. Chem. 2000 , 1091 –1106 .
- 6d G. Zilber , V. Rozenshtein , P.-C. Cheng , L. T. Scott , M. Rabinovitz , H. Levanon , J. Am. Chem. Soc. 1995 , 117 , 10720 –10725 .
- 6e M. Baumgarten , L. Gherghel , M. Wagner , A. Weitz , M. Rabinovitz , P.-C. Cheng , L. T. Scott , J. Am. Chem. Soc. 1995 , 117 , 6254 –6257 .
- 6f A. Ayalon , A. Sygula , P.-C. Cheng , M. Rabinovitz , P. W. Rabideau , L. T. Scott , Science 1994 , 265 , 1065 –1067 .
- 6g P. W. Rabideau , Z. Marcinow , R. Sygula , A. Sygula , Tetrahedron Lett. 1993 , 34 , 6351 –6354 .
- 6h A. Ayalon , M. Rabinovitz , P.-C. Cheng , L. T. Scott , Angew. Chem. Int. Ed. Engl. 1992 , 31 , 1636 –1637 ; Angew. Chem. 1992 , 104 , 1691 .
- 7 A. V. Zabula , A. S. Filatov , S. N. Spisak , A. Y. Rogachev , M. A. Petrukhina , Science 2011 , 333 , 1008 –1011 .
- 8
- 8a S. N. Spisak , A. V. Zabula , M. V. Ferguson , A. S. Filatov , M. A. Petrukhina , Organometallics 2013 , 32 , 538 –543 .
- 8b S. N. Spisak , N. J. Sumner , A. V. Zabula , A. S. Filatov , A. Y. Rogachev , M. A. Petrukhina , Organometallics 2013 , 32 , 3773 –3779 .
- 8c A. V. Zabula , S. N. Spisak , A. S. Filatov , M. A. Petrukhina , Angew. Chem. Int. Ed. 2012 , 51 , 12194 –12198 .
- 8d A. V. Zabula , S. N. Spisak , A. S. Filatov , M. A. Petrukhina , Organometallics 2012 , 31 , 5541 –5545 .
- 8e A. V. Zabula , S. N. Spisak , A. S. Filatov , V. M. Grigoryants , M. A. Petrukhina , Chem. Eur. J. 2012 , 18 , 6476 –6484 .
- 8f S. N. Spisak , A. V. Zabula , A. S. Filatov , A. Y. Rogachev , M. A. Petrukhina , Angew. Chem. Int. Ed. 2011 , 50 , 8090 –8094 .
- 9 C. Bruno , R. Benassi , A. Passalacqua , F. Paolucci , C. Fontanesi , M. Marcaccio , E. A. Jackson , L. T. Scott , J. Phys. Chem. B 2009 , 113 , 1954 –1962 .
- 10 M. A. Petrukhina , L. T. Scott , Dalton Trans. 2005 , 2969 –2975 .
- 11 E. L. Elliott , G. A. Hernandez , A. Linden , J. S. Siegel , Org. Biomol. Chem. 2005 , 3 , 407 –413 .
- 12 B. Zhu , A. Ellern , A. Sygula , R. Sygula , R. J. Angelici , Organometallics 2007 , 26 , 1721 –1728 .
- 13 P. A. Vecchi , C. M. Alvarez , A. Ellern , R. J. Angelici , A. Sygula , R. Sygula , P. W. Rabideau , Organometallics 2005 , 24 , 4543 –4552 .
- 14 P. A. Vecchi , C. M. Alvarez , A. Ellern , R. J. Angelici , A. Sygula , R. Sygula , P. W. Rabideau , Angew. Chem. Int. Ed. 2004 , 43 , 4497 –4500 ; Angew. Chem. 2004 , 116 , 4597 .
- 15 M. Yamada , S. Tashiro , R. Miyake , M. Shionoya , Dalton Trans. 2013 , 42 , 3300 –3303 .
- 16
- 16a R. Maag , B. H. Northrop , A. Butterfield , A. Linden , O. Zerbe , Y. M. Lee , K.-W. Chi , P. J. Stang , J. S. Siegel , Org. Biomol. Chem. 2009 , 7 , 4881 –4885 .
- 16b H. Choi , C. Kim , K.-M. Park , J. Kim , Y. Kang , J. Ko , J. Organomet. Chem. 2009 , 694 , 3529 –3532 .
- 16c H. B. Lee , P. R. Sharp , Organometallics 2005 , 24 , 4875 –4877 .
- 17
- 17a T. J. Kealy , P. L. Pauson , Nature 1951 , 168 , 1039 –1040 .
- 17b S. A. Miller , J. A. Tebboth , J. F. Tremaine , J. Chem. Soc. 1952 , 632 –635 .
- 17c H. Werner , Angew. Chem. Int. Ed. 2012 , 51 , 6052 –6058 .
- 18
- 18a R. C. J. Atkinson, V. C. Gibson , N. J. Long , Chem. Soc. Rev. 2004 , 33 , 313 –328 .
- 18b R. Gómez Arrayás , J. Adrio , J. C. Carretero , Angew. Chem. Int. Ed. 2006 , 45 , 7674 –7715 ; Angew. Chem. 2006 , 118 , 7836 .
- 19 C. Ornelas , New J. Chem. 2011 , 35 , 1973 –1985 .
- 20 Y. Yu , A. D. Bond , P. W. Leonard , U. J. Lorenz , T. V. Timofeeva , K. P. C. Vollhardt , G. D. Whitener , A. A. Yakovenko , Chem. Commun. 2006 , 2572 –2574 .
- 21 A. K. Diallo , C. Absalon , J. Ruiz , D. Astruc , J. Am. Chem. Soc. 2011 , 133 , 629 –641 .
- 22
- 22a A. Hildebrandt , H. Lang , Dalton Trans. 2011 , 40 , 11831 –11837 .
- 22b A. Hildebrandt , D. Schaarschmidt , H. Lang , Organometallics 2011 , 30 , 556 –563 .
- 23
- 23a A. Hildebrandt , H. Lang , Organometallics 2013 , 32 , 5640 –5653 .
- 23b J. M. Speck , R. Claus , A. Hildebrandt , T. Rüffer , E. Erasmus , L. van As , J. C. Swarts , H. Lang , Organometallics 2012 , 31 , 6373 –6380 .
- 23c U. Pfaff , A. Hildebrandt , D. Schaarschmidt , T. Hahn , S. Liebing , J. Kortus , H. Lang , Organometallics 2012 , 31 , 6761 –6771 .
- 23d A. Hildebrandt , D. Schaarschmidt , R. Claus , H. Lang , Inorg. Chem. 2011 , 50 , 10623 –10632 .
- 23e A. Hildebrandt , U. Pfaff , H. Lang , Rev. Inorg. Chem. 2011 , 31 , 111 –141 .
- 23f A. Hildebrandt , T. Rueffer , E. Erasmus , J. C. Swarts , H. Lang , Organometallics 2010 , 29 , 4900 –4905 .
- 24 B. Topolinski , B. M. Schmidt , M. Kathan , S. I. Troyanov , D. Lentz , Chem. Commun. 2012 , 48 , 6298 –6300 .
- 25 B. Topolinski , B. M. Schmidt , S. Higashibayashi , H. Sakurai , D. Lentz , Dalton Trans. 2013 , 42 , 13809 –13812 .
- 26 M. A. Petrukhina , K. W. Andreini , J. Mack , L. T. Scott , J. Org. Chem. 2005 , 70 , 5713 –5716 .
- 27a Y.-T. Wu , D. Bandera , R. Maag , A. Linden , K. K. Baldridge , J. S. Siegel , J. Am. Chem. Soc. 2008 , 130 , 10729 –10739 . 4 -heptanone used instead of 3-pentanone, as originally described for 1,2,5,6-tetrabromocorannulene (8):
- 27b G. Xu , A. Sygula , Z. Marcinow , P. W. Rabideau , Tetrahedron Lett. 2000 , 41 , 9931 –9934 .
- 28 B. M. Schmidt , B. Topolinski , M. Yamada , S. Higashibayashi , M. Shionoya , H. Sakurai , D. Lentz , Chem. Eur. J. 2013 , 19 , 13872 –13880 .
- 29 B. M. Schmidt , S. Seki , B. Topolinski , K. Ohkubo , S. Fukuzumi , H. Sakurai , D. Lentz , Angew. Chem. Int. Ed. 2012 , 51 , 11385 –11388 .
- 30
- 30a L. T. Scott , Pure Appl. Chem. 1996 , 68 , 291 –300 .
- 30b T. J. Seiders , E. L. Elliott , G. H. Grube , J. S. Siegel , J. Am. Chem. Soc. 1999 , 121 , 7804 –7813 .
- 31 C. F. Macrae , I. J. Bruno , J. A. Chisholm , P. R. Edgington , P. McCabe , E. Pidcock , L. Rodriguez-Monge , R. Taylor , J. van de Streek , P. A. Wood , J. Appl. Crystallogr. 2008 , 41 , 466 –470 .
- 32 Persistence of Vision Pty. Ltd., 2004.
- 33
- 33a M. Nishio , CrystEngComm 2004 , 6 , 130 –158 .
- 33b H. Suezawa , T. Yoshida , S. Ishihara , Y. Umezawa , M. Nishio , CrystEngComm 2003 , 5 , 514 –518 .
- 34 Q. Zhang , K. Kawasumi , Y. Segawa , K. Itami , L. T. Scott , J. Am. Chem. Soc. 2012 , 134 , 15664 –15667 .
- 35 For UV spectrum in dichloromethane, see Supporting Information; in ethanol, see: A. A. O. Sarhan, M. S. Ibrahim , M. M. Kamal , K. Mitobe , T. Izumi , Monatsh. Chem. 2009 , 140 , 315 –323 ; in n-hexane, see: W. L. Jolly , The Synthesis and Characterization of Inorganic Compounds, Prentice-Hall, Inc., Englewood Cliffs, 1970 , p. 484–487.
- 36 Y.-L. Wu , M. C. Stuparu , C. Boudon , J.-P. Gisselbrecht , W. B. Schweizer , K. K. Baldridge , J. S. Siegel , F. Diederich , J. Org. Chem. 2012 , 77 , 11014 –11026 .
- 37
R. J. LeSuer
, W. E. Geiger
, Angew. Chem. Int. Ed.
2000
, 39
, 248
–250
; Angew. Chem.
2000
, 112
, 254
.
10.1002/(SICI)1521-3773(20000103)39:1<248::AID-ANIE248>3.0.CO;2-3 CASPubMedWeb of Science®Google Scholar
- 38 A. M. Butterfield , B. Gilomen , J. S. Siegel , Org. Process Res. Dev. 2012 , 16 , 664 –676 .
- 39 S. Jong , TWI 233930(B), 2005 .
- 40 Reactions were run analogously to those described in:
- 40a J. Polin, H. Schottenberger, Org. Synth., Coll. Vol. 1998, 9, 411. J. Polin , H. Schottenberger , Org. Synth. 1996 , 73 , 262; for one-pot synthesis and spectroscopic data, see:
- 40b P. Jutzi , B. Kleinebekel, J. Organomet. Chem. 1997 , 545–546, 573 –576 .
- 41 T. Mochida , K. Takazawa , H. Matsui , M. Takahashi , M. Takeda , M. Sato , Y. Nishio , K. Kajita , H. Mori , Inorg. Chem. 2005 , 44 , 8628 –8641 .
- 42 A. Ambroise , R. W. Wagner , P. D. Rao , J. A. Riggs , P. Hascoat , J. R. Diers , J. Seth , R. K. Lammi , D. F. Bocian , D. Holten , J. S. Lindsey , Chem. Mater. 2001 , 13 , 1023 –1034 .
- 43 G. H. Grube , E. L. Elliott , R. J. Steffens , C. S. Jones , K. K. Baldridge , J. S. Siegel , Org. Lett. 2003 , 5 , 713 –716 .
- 44 K. I. M. Hitoshi , Y. Nakano , EP19970308447, 1997 .
- 45
- 45a SMART: Area-Detector Software Package, Siemens Industrial Automation, Inc., Madison, WI, 1993.
- 45b SAINT Integration Software Package, Siemens Industrial Automation, Inc., Madison, WI, 1993.
- 45c SADABS: Area-Detector Absorption Correction, Siemens Industrial Automation, Inc., Madison, WI, 1996.
- 46 G. Sheldrick , Acta Crystallogr. A 2008 , 64 , 112 –122 .
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